Disperse dyes from heterocyclic acetonitriles

ABSTRACT

Disclosed are disperse dyes for the dyeing of synthetic fibers such as cellulose acetate, triacetate, polyamide, and especially polyester and its blends, which have the general formula ##STR1## in which R 1  is selected from hydrogen, aryl, cyclohexyl, lower alkyl and lower alkyl substituted by Cl, CN, OC 2  H 4  OC 2  H 5 , ##STR2## lower alkoxy, aryl, NHCONHPh, OCONHPh, phthalimido, succinimido, or aryloxy, which aryloxy may be substituted by one or more of Cl, Br, NO 2 , CN, lower alkyl, lower alkoxy, aryl and aryloxy; R 2  is phenyl or phenyl substituted with 1-3 of lower alkyl, lower alkoxy, ##STR3## --CN, --Cl or --NO 2  ; R 3  is H, Cl, lower alkyl or lower alkoxy; R 1  and R 3  may form a 5 or 6 membered ring preferably substituted by 1-3 methyl groups; R 4  is H, Cl, lower alkyl or lower alkoxy; R 5  is selected from 3-pyridyl, 3-benzisothiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, 2-quinoxalyl, 2-quinazolinonyl, 2-1,3,4-oxadiazolyl, 2-1,3,4-thiadiazolyl and 2-thienyl, which R 5  heterocycles may be substituted by Cl, Br, NO 2 , CN, aryl, aryl substituted by Cl, Br, NO 2  or CN, lower alkyl or COOR 6  wherein R 6  is lower alkyl or aryl; and n is 1-4.

This invention concerns novel heterocyclic methine dyes prepared for example from heterocyclc acetonitriles and formylated compounds, and their use in dyeing synthetic fibers such as polyester and cellulosics. These dyes give deep yellow or orange to neutral yellow shades of excellent fastness properties and dyeability.

The dyes have the formula ##STR4## in which R₁ is selected from hydrogen, aryl, cyclohexyl, lower alkyl and lower alkyl substituted by Cl, CN, OC₂ H₄ OC₂ H₅, ##STR5## lower alkoxy, aryl, NHCONHPh, OCONHPh, phthalimido, succinimido, or aryloxy, which aryloxy may be substituted by one or more of Cl, Br, NO₂, CN, lower alkyl, lower alkoxy, aryl and aryloxy; R₂ is phenyl or phenyl substituted with 1-3 of lower alkyl, lower alkoxy, ##STR6## --CN, --Cl or --NO₂ ; R₃ is H, Cl, lower alkyl or lower alkoxy; R₁ and R₃ may form a 5 or 6 membered ring preferably substituted by 1-3 methyl groups; R₄ is H, Cl, lower alkyl or lower alkoxy; R₅ is selected from 3-pyridyl, 3-benzisothiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, 2-quinoxalyl, 2-quinazolinonyl, 2-1,3,4-oxadiazolyl, 2-1,3,4-thiadiazolyl and 2-thienyl, which heterocycles may be substituted by Cl, Br, NO₂, CN, aryl, aryl substituted by Cl, Br, NO₂ or CN, lower alkyl or COOR₆ wherein R₆ is lower alkyl or aryl. The term "lower" as used herein means 1-6 carbons.

The present dyes have outstanding pH stability, color strength, fastness and dyeing properties, for the conventional dyeing of polyester fiber and its blends, and other synthetic fibers e.g. cellulose acetate, triacetate, and the like. The dyes also have good pH stability in the dyebath, good sublimation and lightfastness properties, and show little or no variation in shade or strength when dyed at 110° and 130° on polyester. The dyes also have improved color strength when compared with other commonly used dyes e.g. C. I. Disperse Yellow 54. Methine dyes which have found value in the dyeing of polyester are generally greenish yellow in shade, but the methine dyes of this invention are normally orange to neutral yellow in shade.

The dyeing of the fiber material mentioned with the dyestuffs according to the invention is appropriately carried out from an aqueous suspension in the presence of carriers at between 80° and 110° C., in the absence of carriers at between 100°-130° C., or using the so-called thermofixing process at 180°-230° C. The printing of the materials can be carried out by steaming the goods, printed with the new dyestuffs, in the presence of a carrier at temperatures between 80° C. and 110° C. or also in the absence of a carrier at 110°-140° C., or also by treating the goods, printed with the new dyestuffs, according to the so-called thermofixing process at 180°-230° C.

This invention will be further illustrated by the following example although it will be understood that this example is included merely for purposes of illustration and is not intended to limit the scope of the invention.

EXAMPLE 1

4-Formyl-N-ethyl-N-(β-4-methoxy phenoxy ethyl)-3-methylaniline (1.565 g, 0.005 mole) was dissolved in ethyl alcohol (40 ml). To this was added 2-benzothiazoleacetonitrile (0.85 g, 0.005 mole) and piperidine (0.1 ml) and the mixture was warmed on a steam bath for 15 minutes, then left to cool overnight. The orange crystalline product was collected by filtration and air dried. The dye was ball milled in the presence of a lignin sulphonate dispersing agent for 24 hours and the resulting dispersion was applied to polyester fiber by dyeing at 130° for 1 hour. It gave a deep yellow dyeing of excellent color strength and fastness. Similar dyeings prepared in dyebaths buhfered from pH 4-8 also gave high strength dyeings indicating the dye had excellent pH stability.

By application of the synthetic procedures outlined in Example 1, the following dyes of the general formula shown where n is 2, were prepared. When applied by a procedure similar to the above they gave high strength dyeings on polyester fiber.

    __________________________________________________________________________      ##STR7##                                                                      Example                                                                             R.sub.1   R.sub.2     R.sub.3                                                                            R.sub.4                                                                            R.sub.5                                     __________________________________________________________________________     2    C.sub.6 H.sub.11                                                                          ##STR8##   H   H   benzothiazolyl                              3    CH.sub.2 C.sub.6 H.sub.5                                                                 "           "   "   benzoxazolyl                                4    Me                                                                                        ##STR9##   "   "   benzothiazolyl                              5    Et                                                                                        ##STR10##  Me  Me  benzothiazolyl                              6    "         "           "   "   benzoxazolyl                                7    C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                         ##STR11##  H   "   benzothiazolyl                              8    "         "           "   "   benzoxazolyl                                      ##STR12##                                                                                ##STR13##  "   "   benzothiazolyl                              10   "         "           "   "   benzoxazolyl                                11   C.sub.3 H.sub.7                                                                           ##STR14##  "   "   benzoxazolyl                                12                                                                                   ##STR15##                                                                                ##STR16##  "   "   benzothiazolyl                              13   CH.sub.3                                                                                  ##STR17##  "   "   benzothiazolyl                              14   "                                                                                         ##STR18##  "   "   benzothiazolyl                              15   "                                                                                         ##STR19##  "   "   benzothiazolyl                              16   C.sub.2 H.sub.4 CN                                                                        ##STR20##  H   CH.sub.3                                                                           5-chloro- benzoxazolyl                      17                                                                                   ##STR21##                                                                               "           H   CH.sub.3                                                                           3-benziso- thiazolyl                        18   C.sub.2 H.sub.4 OPh                                                                       ##STR22##  H   CH.sub.3                                                                           3-benziso- thiazolyl                        19   C.sub.2 H.sub.4 NHCONHPh                                                                  ##STR23##  H   CH.sub.3                                                                           5-cyano- benzoxazolyl                       20   CH.sub.3  "           H   CH.sub.3                                                                           3-pyridyl                                   21   CH.sub.3                                                                                  ##STR24##  H   H   5-bromo- benzoxazolyl                       22   C.sub.2 H.sub.4 CN                                                                       "           H   H   5-nitro-                                                                       benzoxazolyl                                23   C.sub.2 H.sub.5                                                                           ##STR25##  H   CH.sub.3                                                                           3-pyridyl                                   24   C.sub.2 H.sub.4                                                                          "           CH.sub.3                                                                           OCH.sub.3                                                                          "                                           25   C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                         ##STR26##  CH.sub.3                                                                           OCH.sub.3                                                                          "                                           26   C.sub.2 H.sub.5                                                                           ##STR27##  Cl  Cl  "                                           27   C.sub.2 H.sub.5                                                                           ##STR28##  H   H   5-cyano- benzoxazolyl                       28   C.sub.2 H.sub.5                                                                           ##STR29##  H   H   5-cyano- benzoxazolyl                       29   C.sub.2 H.sub.4 OPhp-OCH.sub.3                                                            ##STR30##  H   H   5-methyl- benzoxazolyl                      30                                                                                   ##STR31##                                                                                ##STR32##  CH.sub.3                                                                           CH.sub.3                                                                           5-COOCH.sub.3 benzoxazolyl                  31   C.sub.2 H.sub.5                                                                          "           CH.sub.3                                                                           CH.sub.3                                                                           2-quinoxalyl                                32   CH.sub.2 C.sub.6 H.sub.5                                                                  ##STR33##  H   CH.sub.3                                                                           5-nitro- benzoxazolyl                       33   C.sub.2 H.sub.5                                                                           ##STR34##  H   CH.sub.3                                                                           2-quinoxalyl                                34   C.sub.2 H.sub.5                                                                          "           H   CH.sub.3                                                                           "                                           35   H                                                                                         ##STR35##  OC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   "                                           36   C.sub.2 H.sub.4 CN                                                                       "           H   CH.sub.3                                                                           5-chloro-                                                                      benzothiazolyl                              37                                                                                   ##STR36##                                                                                ##STR37##  H   CH.sub.3                                                                           5-chloro- benzothiazolyl                    38   C.sub.2 H.sub.5                                                                          "           H   CH.sub.3                                                                           2-quinoxalyl                                39   C.sub.2 H.sub.5                                                                           ##STR38##  H   CH.sub.3                                                                           "                                           40   C.sub.2 H.sub.4 OCONHPh                                                                   ##STR39##  H   CH.sub.3                                                                           "                                           41   C.sub.6 H.sub.11                                                                          ##STR40##  H   H   "                                           42   C.sub.2 H.sub.4 CN                                                                        ##STR41##  H   H   5-nitro- benzothiazolyl                     43   C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                         ##STR42##  H   CH.sub.3                                                                           2-Quinazolinonyl                            44   C.sub.2 H.sub.4 Cl                                                                        ##STR43##  CH.sub.3                                                                           OCH.sub.3                                                                          "                                           45   C.sub.2 H.sub.4 Cl                                                                       "           CH.sub.3                                                                           OCH.sub.3                                                                          "                                           46   C.sub.6 H.sub.11                                                                          ##STR44##  Cl  Cl  "                                           47   C.sub.2 H.sub.4 OPhp-Cl                                                                   ##STR45##  H   H   5-cyano- benzothiazolyl                     48   C.sub.2 H.sub.4 OPhp-NO.sub.2                                                            "           H   H   5-cyano-                                                                       benzothiazolyl                              49   C.sub.2 H.sub.4 OPhp-OCH.sub.3                                                            ##STR46##  H   H   5-methyl- benzothiazolyl                    50   C.sub.2 H.sub.4 OCONHPh                                                                  "           CH.sub.3                                                                           CH.sub.3                                                                            5-COOCH.sub.3                                                                 benzothiazolyl                              51   C.sub.2 H.sub.5                                                                           ##STR47##  CH.sub.3                                                                           CH.sub.3                                                                           5-COOCH.sub.3 benzothiazolyl                52                                                                                   ##STR48##                                                                               "           H   CH.sub.3                                                                           5-nitro- benzothiazolyl                     53   C.sub.2 H.sub.4 OPh                                                                       ##STR49##  H   CH.sub.3                                                                           5-nitro- benzothiazolyl                     54   C.sub.2 H.sub.4 NHCONHPh                                                                  ##STR50##  H   CH.sub.3                                                                           5-nitro- benzothiazolyl                     55   C.sub.2 H.sub.4 Ph                                                                        ##STR51##  OC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   5-nitro- benzothiazolyl                     56   C.sub.2 H.sub.4 CN                                                                        ##STR52##  H   CH.sub.3                                                                           5-phenyl-1,3,4- oxadiazolyl                 57                                                                                   ##STR53##                                                                                ##STR54##  H   CH.sub.3                                                                           2-1,3,4-thiadiazolyl                        58   C.sub.2 H.sub.5                                                                           ##STR55##  H   CH.sub.3                                                                           "                                           59   C.sub.6 H.sub.5                                                                          "           H   CH.sub.3                                                                           "                                           60   C.sub.6 H.sub.5                                                                           ##STR56##  H   CH.sub.3                                                                           "                                           61   CH.sub.3                                                                                  ##STR57##  H   H   "                                           62   C.sub.2 H.sub.4 CN                                                                       "           H   H   2-thienyl                                   63   C.sub.2 H.sub.4 CN                                                                        ##STR58##  H   CH.sub.3                                                                           "                                           64   CH.sub.2 Cl                                                                              "           CH.sub.3                                                                           OCH.sub.3                                                                          "                                           65   H                                                                                         ##STR59##  CH.sub.3                                                                           OCH.sub.3                                                                          "                                           66   C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         "           Cl  Cl  "                                           67   C.sub.2 H.sub.4 OPhp-Br                                                                   ##STR60##  H   H   "                                           68   C.sub.2 H.sub.4 OPhp-CN                                                                   ##STR61##  H   H   "                                           69   C.sub.2 H.sub.4 OPhp-OCH.sub.3                                                            ##STR62##  H   H   3-benziso- thiazolyl                        70   C.sub.2 H.sub.4 OPhp-CN                                                                   ##STR63##  CH.sub.3                                                                           CH.sub. 3                                                                          3-benziso- thiazolyl                        71   C.sub.2 H.sub.4 OCONHPh                                                                   ##STR64##  CH.sub.3                                                                           CH.sub.3                                                                           3-benziso- thiazolyl                        72   CH.sub.2 C.sub.6 H.sub.5                                                                  ##STR65##  H   CH.sub.3                                                                           3-benziso- thiazolyl                        73   C.sub.2 H.sub.4 OPhp-CH.sub.3                                                            "           H   CH.sub.3                                                                           3-benziso-                                                                     thiazolyl                                   74   C.sub.2 H.sub.4 NHCONHPh                                                                  ##STR66##  H   CH.sub.3                                                                           3-benziso- thiazolyl                        75   C.sub.2 H.sub.4 Ph                                                                        ##STR67##  OC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   3-benziso- thiazolyl                        76   C.sub.2 H.sub.4 OPhp-OPh                                                                  ##STR68##  H   H   2-1,3,4-oxadiazolyl                         77   C.sub.2 H.sub.4 OPhp-OCH.sub.3                                                            ##STR69##  H   H   "                                           78   C.sub.2 H.sub.4 OPhp-Ph                                                                   ##STR70##  CH.sub.3                                                                           CH.sub.3                                                                           "                                           79   C.sub.2 H.sub.4 OCONHPh                                                                   ##STR71##  CH.sub.3                                                                           CH.sub.3                                                                           "                                           80   C.sub.6 H.sub.11                                                                          ##STR72##  H   CH.sub.3                                                                           "                                           81   C.sub.2 H.sub.4 OPh                                                                      "           H   CH.sub.3                                                                           "                                           82   C.sub.2 H.sub.4 NHCONHPh                                                                  ##STR73##  H   CH.sub.3                                                                           "                                           83   C.sub.2 H.sub.4 Ph                                                                        ##STR74##  OC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   "                                           __________________________________________________________________________

Also, the dyes of the formula below are prepared by procedures similar to Example 1 ##STR75##

    ______________________________________                                         Example R.sub.2          R.sub.4 R.sub.5                                       ______________________________________                                         84                                                                                                      H       benzothiazolyl                                85                                                                                      ##STR76##       "       benzoxazolyl                                  86                                                                                      ##STR77##       "       5-phenyl 1,3, 4-oxadiazolyl                   87                                                                                      ##STR78##       "       benzothiazolyl                                88      "                "       benzoxazolyl                                  89                                                                                      ##STR79##       "       benzothiazolyl                                90      "                "       benzoxazolyl                                  91                                                                                      ##STR80##       "       benzothiazolyl                                92      "                "       benzoxazolyl                                  93                                                                                      ##STR81##       "       benzothiazolyl                                94      "                "       benzoxazolyl                                  95                                                                                      ##STR82##       Me      benzothiazolyl                                96      "                "       benzoxazolyl                                  97      "                "       5-phenyl-1,3,                                                                  4-oxadiazolyl                                 98                                                                                      ##STR83##       "       benzothiazolyl                                99      "                "       benzoxazolyl                                  100     "                "       5-phenyl-1,3,                                                                  4-oxadiazolyl                                 101                                                                                     ##STR84##       "       benzothiazolyl                                102                                                                                     ##STR85##       "       benzoxazolyl                                  103     "                "       5-phenyl-1,3,                                                                  4-oxadiazolyl                                 104                                                                                     ##STR86##       H       5-chloro-   benzoxazolyl                      105                                                                                     ##STR87##       CH.sub.3                                                                               5-chloro- benzoxazolyl                        106     "                H       5-chloro-                                                                      benzoxazolyl                                  107                                                                                     ##STR88##       H       5-chloro- benzoxazolyl                        108                                                                                     ##STR89##       H       5-chloro- benzoxazolyl                        109     "                CH.sub.3                                                                               5-chloro-                                                                      benzoxazolyl                                  110                                                                                     ##STR90##       H       5-chloro- benzoxazolyl                        111     "                H       5-chloro-                                                                      benzoxazolyl                                  112                                                                                     ##STR91##       H       5-chloro- benzoxazolyl                        113     "                H       5-chloro-                                                                      benzothiazolyl                                114                                                                                     ##STR92##       CH.sub.3                                                                               5-chloro- benzothiazolyl                      115     "                H       5-chloro-                                                                      benzothiazolyl                                116                                                                                     ##STR93##       H       5-chloro- benzothiazolyl                      117     "                H       5-chloro-                                                                      benzothiazolyl                                118     "                CH.sub.3                                                                               5-chloro-                                                                      benzothiazolyl                                119                                                                                     ##STR94##       H       5-chloro- benzothiazolyl                      120     "                H       5-chloro-                                                                      benzothiazolyl                                121                                                                                     ##STR95##       H       5-chloro- benzothiazolyl                      122                                                                                     ##STR96##       H       5-phenyl-1,3,4- oxadiazolyl                   123     "                CH.sub.3                                                                               5-phenyl-1,3,4-                                                                oxadiazolyl                                   124                                                                                     ##STR97##       H       5-phenyl-1,3,4- oxadiazolyl                   125                                                                                     ##STR98##       H       5-phenyl-1,3,4- oxadiazolyl                   126     "                H       5-phenyl-1,3,4-                                                                oxadiazolyl                                   127                                                                                     ##STR99##       CH.sub.3                                                                               5-phenyl-1,3,4- oxadiazolyl                   128     "                H       5-phenyl-1,3,4-                                                                oxadiazolyl                                   129                                                                                     ##STR100##      H       5-phenyl-1,3,4- oxadiazolyl                   130     "                Cl      5-phenyl-1,3,4-                                                                oxadiazolyl                                   131                                                                                     ##STR101##      H       3-pyridyl                                     132                                                                                     ##STR102##      CH.sub.3                                                                               "                                             133     "                H       "                                             134                                                                                     ##STR103##      H       "                                             135                                                                                     ##STR104##      H       "                                             136     "                CH.sub.3                                                                               "                                             137                                                                                     ##STR105##      OCH.sub.3                                                                              "                                             138     "                H       "                                             139                                                                                     ##STR106##      H       "                                             140     "                H       "                                             141                                                                                     ##STR107##      CH.sub.3                                                                               "                                             142     "                H       "                                             143                                                                                     ##STR108##      H       "                                             144     "                H       "                                             145     "                CH.sub.3                                                                               "                                             146                                                                                     ##STR109##      H       "                                             147     "                H       "                                             148                                                                                     ##STR110##      Cl      3- benzisothiazolyl                           149                                                                                     ##STR111##      CH.sub.3                                                                               3- benzisothiazolyl                           150     "                H       3-                                                                             benzisothiazolyl                              151                                                                                     ##STR112##      H       3- benzisothiazolyl                           152                                                                                     ##STR113##      H       3- benzisothiazolyl                           153     "                CH.sub.3                                                                               3-                                                                             benzisothiazolyl                              154                                                                                     ##STR114##      H       3- benzisothiazolyl                           155     "                H       3-                                                                             benzisothiazolyl                              156                                                                                     ##STR115##      H       3- benzisothiazolyl                           157     "                H       3-                                                                             benzisothiazolyl                              158                                                                                     ##STR116##      CH.sub.3                                                                               3- benzisothiazolyl                           159     "                H       3-                                                                             benzisothiazolyl                              160                                                                                     ##STR117##      H       3- benzisothiazolyl                           161     "                H       3-                                                                             benzisothiazolyl                              162     "                CH.sub.3                                                                               3-                                                                             benzisothiazolyl                              163                                                                                     ##STR118##      H       3- benzisothiazolyl                           164     "                OCH.sub.3                                                                              3-                                                                             benzisothiazolyl                              165                                                                                     ##STR119##      H       2-quinoxalyl                                  166                                                                                     ##STR120##      CH.sub.3                                                                               "                                             167     "                H       "                                             168                                                                                     ##STR121##      H       "                                             169                                                                                     ##STR122##      H       "                                             170     "                CH.sub.3                                                                               "                                             171                                                                                     ##STR123##      H       "                                             172     "                H       "                                             173                                                                                     ##STR124##      H       "                                             174     "                H       "                                             175                                                                                     ##STR125##      CH.sub.3                                                                               "                                             176     "                H       "                                             177                                                                                     ##STR126##      Cl      "                                             178     "                H       "                                             179     "                CH.sub.3                                                                               "                                             180                                                                                     ##STR127##      H       "                                             181     "                H       "                                             182                                                                                     ##STR128##      H       2-quinazolinonyl                              183                                                                                     ##STR129##      CH.sub.3                                                                               "                                             184     "                H       "                                             185                                                                                     ##STR130##      H       "                                             186                                                                                     ##STR131##      H       "                                             187     "                CH.sub.3                                                                               "                                             188                                                                                     ##STR132##      OCH.sub.3                                                                              "                                             189     "                H       "                                             190                                                                                     ##STR133##      H       "                                             191     "                H       "                                             192                                                                                     ##STR134##      CH.sub.3                                                                               "                                             193     "                H       "                                             194                                                                                     ##STR135##      H       "                                             195     "                H       "                                             196     "                CH.sub.3                                                                               "                                             197                                                                                     ##STR136##      H       "                                             198     "                H       "                                             199                                                                                     ##STR137##      H       2-1,3,4-oxa- diazolyl                         200                                                                                     ##STR138##      CH.sub.3                                                                               2-1,3,4-oxa- diazolyl                         201     "                H       2-1,3,4-oxa-                                                                   diazolyl                                      202                                                                                     ##STR139##      H       2-1,3,4-oxa- diazolyl                         203                                                                                     ##STR140##      H       2-1,3,4-oxa- diazolyl                         204     "                CH.sub.3                                                                               2-1,3,4-oxa-                                                                   diazolyl                                      205                                                                                     ##STR141##      H       2-1,3,4-oxa- diazolyl                         206     "                H       2-1,3,4-oxa-                                                                   diazolyl                                      207                                                                                     ##STR142##      H       2-1,3,4-oxa- diazolyl                         208     "                H       2-1,3,4-oxa-                                                                   diazolyl                                      209                                                                                     ##STR143##      CH.sub.3                                                                               2-1,3,4-oxa- diazolyl                         210     "                H       2-1,3,4-oxa-                                                                   diazolyl                                      211                                                                                     ##STR144##      H       2-1,3,4-oxa- diazolyl                         212     "                H       2-1,3,4-oxa-                                                                   diazolyl                                      213     "                CH.sub.3                                                                               2-1,3,4-oxa-                                                                   diazolyl                                      214                                                                                     ##STR145##      H       2-1,3,4-oxa- diazolyl                         215     "                H       2-1,3,4-oxa-                                                                   diazolyl                                      216                                                                                     ##STR146##      H       2-1,3,4-thia- diazolyl                        217                                                                                     ##STR147##      CH.sub.3                                                                               2-1,3,4-thia- diazolyl                        218     "                H       2-1,3,4-thia-                                                                  diazolyl                                      219                                                                                     ##STR148##      H       2-1,3,4-thia- diazolyl                        220                                                                                     ##STR149##      H       2-1,3,4-thia- diazolyl                        221     "                CH.sub.3                                                                               2-1,3,4-thia-                                                                  diazolyl                                      222                                                                                     ##STR150##      H       2-1,3,4-thia- diazolyl                        223     "                H       2-1,3,4-thia-                                                                  diazolyl                                      224                                                                                     ##STR151##      H       2-1,3,4-thia- diazolyl                        225     "                H       2-1,3,4-thia-                                                                  diazolyl                                      226                                                                                     ##STR152##      CH.sub.3                                                                               2-1,3,4-thia- diazolyl                        227     "                H       2-1,3,4-thia-                                                                  diazolyl                                      228                                                                                     ##STR153##      H       2-1,3,4-thia- diazolyl                        229     "                H       2-1,3,4-thia-                                                                  diazolyl                                      230     "                CH.sub.3                                                                               2-1,3,4-thia-                                                                  diazolyl                                      231                                                                                     ##STR154##      OCH.sub.3                                                                              2-1,3,4-thia- diazolyl                        232     "                H       2-1,3,4-thia-                                                                  diazolyl                                      233                                                                                     ##STR155##      H       2-thienyl                                     234                                                                                     ##STR156##      CH.sub.3                                                                               "                                             235     "                H       "                                             236                                                                                     ##STR157##      H       "                                             237                                                                                     ##STR158##      Cl      "                                             238     "                CH.sub.3                                                                               "                                             239                                                                                     ##STR159##      H       "                                             240     "                H       "                                             241                                                                                     ##STR160##      H       "                                             242     "                H       "                                             243                                                                                     ##STR161##      CH.sub.3                                                                               "                                             244     "                H       "                                             245                                                                                     ##STR162##      H       "                                             246     "                H       "                                             247     "                CH.sub.3                                                                               "                                             248                                                                                     ##STR163##      H       "                                             249     "                H       "                                             ______________________________________                                    

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

I claim:
 1. A compound of the formula ##STR164## in which R₁ is selected from hydrogen, aryl cyclohexyl, lower alkyl and lower alkyl substituted with Cl, CN, OC₂ H₄ OC₂ H₅, ##STR165## lower alkoxy, aryl, NHCONHPh, OCONHPh, phthalimido, succinimido, aryloxy and aryloxy substituted with one or more of Cl, Br, NO₂, CN, lower alkyl, lower alkoxy, aryl and aryloxy; R₂ is phenyl or phenyl substituted with 1-3 of lower alkyl, lower alkoxy, ##STR166## --CN, --Cl or --NO₂ ; R₃ is H, Cl, lower alkyl or lower alkoxy; R₁ and R₃ combined form --CH₂ CH₂ CH₂ -- unsubstituted or substituted with 1-3 methyl groups; R₄ is H, Cl, lower alkyl or lower alkoxy; R₅ is selected from 3-pyridyl, 3-benzisothiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, 2-quinoxalyl, 2-quinazolinonyl, 2-1,3,4-oxadiazolyl, 2-1,3,4-thiadiazolyl and 2-thienyl, which R₅ heterocycles are unsubstituted or substituted with Cl, Br, NO₂, CN, aryl, aryl substituted with Cl, Br, NO₂ or CN, lower alkyl, or COOR₆ wherein R₆ is lower alkyl or aryl; and n is 1-4.
 2. A compound according to claim 1 having the formula ##STR167##
 3. A compound according to claim 1 having the formula ##STR168##
 4. A compound according to claim 1 having the formula ##STR169##
 5. A compound according to claim 1 havng the formula ##STR170## 